Process for the preparation of monocyclic ketones and their alkyl derivatives havingmore than nine ring members



Patented Feb. 19, 1929.

UNITED STATES 1,702,845 PATIENT OFFICE.

LEOPOLD RUZIC'KA, OF GENEVA, SWITZERLAND, ASSIGNOR TO K. NARI 8; (10-,OF GENEVA, SWITZERLAND, A COMPANY OF SWITZERLAND.

rnocnss FOB lflo Drawing. Application filed November 19,

THE PREPARATION OF MONOCYCLIO KETONES AND THEIR ALKYL DE- RIVATIYESHAVING MORE THAN NINE RING MEMBERS.

1926, Serial no. 149,537, and in Switzerland December In the priorapplication Serial No. 36,049 filed June 9, 1925, there is described aprocess of preparing monocyclic ketones having more than nine ringmembers, which comprises heating a normal straight chain aliphaticdicarboxylic acid salt of the fourth group of the periodic systemespecially thorium and cerium, said acid having a carbon chaincontaining more than ten carbon atoms, the carboxylic acid groups beinglinked to the end carbons thereof.

It has also been discovered that in a general manner for the preparationof monocyclic ketones havin more than nine ring members and of theiralkyl derivatives, from the dicarboxylic acids having more than tencarbon atoms in a normal chain or from their alkyl derivatives, themetals and the compounds of metals belonging to the third group of theperiodic system may advantageously be employed.

Accordingto the present invention yttrium which belongs to the saidmetals, or its compounds such as for instance yttrium oxide 2 areemployed either alone or mixed with another metal or metal compoundbelonging to the saidthird group of the periodic system. It is alsoadvantageous to use a mixture of several metals of the fourth group ofthe periodic system or of the rare earths, these mixtures being obtainedartificially or other- Mixtures of the 'above mentioned dicarof theiralkyl derivatives, preboxylic acids pared from the pure acids or as theyareob- The pure 3-methyl-cyclopentadecanone can,

compounds.

y E'mamplell. 8 methyl tetradeeane-l 1.1a dicarboxylic with acids theacid is heated crystallization in,

tained in certain technical methods or from natural products give,according to the present invention, mixtures of the ketones, or theiralkyl derivatives, which, in this form can also be employed in practice.

For obtaining the mentioned monocyclic ketones, it is possible to heatdirectly the acids or the acid anhydrides alone or in presence of metalsor metal compounds at a comparatively high temperature, instead of firsttransforming the corresponding dicar-' boxyhc acids into salts. In thiscase the use of metals of the third group of the periodic system is alsoadvantageous.

The ketones or their alkyl derivatives obtamed by the described processcan be used as perfumes or as primaiynilnaterials for the preparation ofother tec 'ca-lly important compounds.

Example 1.

The yttrium salt of 3-methyl-tetradecane- 1, l-dicarboxylic acid isheated, preferably I other reagent usually employed for isolating theketones.

The formation of the 3-methyl-cyclo tadecanone can be represented by the0 ow-'v ing equation:

centigrade and towards the end of the reaction preferably in a vacuumwith yttrium h droxide m a quantity which does not su as for "completelyconverting the acid into thenorup to above 300 to 500 degrees 7 malsalt. The product obtained is treated ac cording to the method describedin. Example 1. y

A mixture of the yttrium anderbium salts of4:-methyltetradecane-1.14-dicarbo lic acid I in Exis heated and workedup as deecri obtained boils at ample l. The l-methyl-cyclopentadecanoneabout 125 C. (at 0.3 mm),

ives asemicarbazone melting at about 166 5%. and has a smell like thatof natural musk and can therefore be used as a perfume and for preparingother interesting technical compounds.

Example 4.

l methyl tetradecane 1.1a dicarboxylic acid is heated at about 300 to500 C. and towards the end of the reaction preferably in a Vacuum, withyttrium oxide. The product obtained is worked up as described in Examboxylic acid is heated to about 300 to 500 1 a. vacuum with worked up asdm cribed in Example 5.

ple 3.

Ewample 5.

The yttrium salt of tetradecane-LM-dicarboxylic acid is heated andworked up as described in Example 1. The cyclo-pentadecanone is obtainedwhich distills at about 120 C. (at 0.3 mm.) and melts at 63 C.

7 Example 6.

Tetradecane-l.ll-dicarboxylic acid is heated at about 300 to 500 0.,towards the end of the reaction preferably in vacuum, with yttriumhydroxide. The distillate resulting therefrom is worked up as describedin Example 5.

Ereample 7.

The anhydride of tetradecane-1.14 dicar- C. preferably in yttriumhydroxide and towards the end of the reaction Example 8.

An yttrium salt of tetradecane-LM-dicarboxylic acid is prepared bypartially neutralizing this dicarboxylic acid with sodium hydroxide andprecipitating with yttriumchloride. The resulting yttrium salt isdecomposed by heating and worked up as described in Example 5.

Pinnacle Emample .9.

The yttrium salt of octadecane-l.l8-dicarboxylic acid is heatedpreferably in a vacuum to about 300 to 500 C. and the resultingdistillate is worked u by fractional distillation. The fraction distiling at from 140 to 180 C. (at 0.3 mm.) is then treated withsemicarbazide or other reagent usually employed for isolating theketones. The cyclononadecanone in a pure state can in this manner heisolated by treating the semicarbazone purified by crystallization fromalcohol and melting at 184 (1. This ketone boils at 160 mm), melts at 72C. and has a smell which nearly corresponds to that of civetone. It cantherefore be used as a perfume and as a primary material for preparingother interesting technical compounds; by oxidizing thecyclononadecanone with chromic acid hcptadecane-1.17-dicarboxylic acidis formed.

Ewample 10.

A mixture of cyclopentadecanone and cyclohexadecanone is obtained byworking up according to the method described in Exanr ple 1 a mixture ofyttriumand erbium salts of tetradecane-l.ll-dicarboxylic andpentadecane-l.15-dicarboxylic acid.

I claim:

1. A process for the preparation of monocyclic ketones having more thannine ring members comprising heating yttrium salts of LEOPOLD RUzrcKA,

salts of polymethyl-

